EP2937338B1 - Procédé et dispositif de production d'un composé d'halohydrantoïne, système réutilisable, et composé d'halohydrantoïne - Google Patents

Procédé et dispositif de production d'un composé d'halohydrantoïne, système réutilisable, et composé d'halohydrantoïne Download PDF

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EP2937338B1
EP2937338B1 EP13864692.2A EP13864692A EP2937338B1 EP 2937338 B1 EP2937338 B1 EP 2937338B1 EP 13864692 A EP13864692 A EP 13864692A EP 2937338 B1 EP2937338 B1 EP 2937338B1
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Prior art keywords
dryer
composition
organic solvent
pressure
compound
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German (de)
English (en)
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EP2937338A4 (fr
EP2937338A1 (fr
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Tomohiro Ikegami
Yukihiko Hanamura
Shinji UCHIKOSHI
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Nippon Kasei Chemical Co Ltd
Nippoh Chemicals Co Ltd
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Nippon Kasei Chemical Co Ltd
Nippoh Chemicals Co Ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/06—Flash distillation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D3/00—Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/007—Energy recuperation; Heat pumps
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/74—Two oxygen atoms, e.g. hydantoin with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to other ring members
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
    • C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
    • C07D233/66—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D233/72—Two oxygen atoms, e.g. hydantoin
    • C07D233/80—Two oxygen atoms, e.g. hydantoin with hetero atoms or acyl radicals directly attached to ring nitrogen atoms
    • C07D233/82—Halogen atoms

Definitions

  • the present invention relates to a method and the use of an apparatus each for producing a halohydantoin compound, and a recycling process.
  • Halohydantoin compounds have been widely used as a sensitizer for a photograph or the like or as a halogenating agent or an oxidizing agent for use in a process of producing a medicinal product, an agricultural chemical, a chemical compound, or the like.
  • the halohydantoin compounds are considered as a promising compound because the halohydantoin compounds are stable and can be more economically produced by a known method.
  • One of such halohydantoin compounds is 1,3-diiodo-5,5-dimethylhydantoin.
  • a method for producing 1,3-diiodo-5,5-dimethylhydantoin for example, a method including the step of causing 5,5-dimethylhydantoin and iodine monochloride to react with each other in the presence of a base in a mixed solvent of an aqueous solution of a base and an organic solvent and a refining method have been disclosed (see, for example, Patent Literature 1 and Non-Patent Literature 1).
  • Non-Patent Literature 1 describes the following method: 5,5-dimethylhydantoin and iodine monochloride are reacted with each other with use of a sodium hydroxide aqueous solution and carbon tetrachloride. The resulting crystals are washed with water, and are further washed with anhydrous ethyl acetate. After that, the crystals are dried at 60°C under a reduced pressure and thereby, 1,3-diiodo-5,5-dimethylhydantoin is refined.
  • Non-Patent Literature 1 further states that the resulting 1,3-diiodo-5,5-dimethylhydantoin is a reagent so stable that it can be preserved without recrystallizing in a desiccator in a dark place.
  • Patent Literature 1 gives the following description: First, 5,5-dimethylhydantoin and iodine monochloride are reacted with each other in a sodium hydroxide aqueous solution with use of N,N-dimethylformamide or an n-butyl acetate solvent. Next, the precipitated crystals as a result of the reaction are collected by filtration, and then, dried in one step under a reduced pressure, thereby being refined.
  • Patent Literature 2 describes a method for producing a 1,3-diiodohydantoin compound comprising the steps of providing a wet material containing the 1,3-diiodohydantoin compound, and either one step of (1) contacting the wet material with a heated air to dry the wet material or one step of (2) lyophilizing the wet material.
  • Patent literature 3 teaches a method for preparing halohydantoin compounds, and drying the wet compound in one step under reduced pressure.
  • 1,3-diiodo-5,5-dimethylhydantoin contains 65% of effective iodine, and the yield of 1,3-diiodo-5,5-dimethylhydantoin is as low as 75%.
  • Non-Patent Literature 1 makes no mention of the purity of 1,3-diiodo-5, 5-dimethylhydantoin.
  • Patent Literature 1 makes no mention of the purity of 1,3-diiodo-5,5-dimethylhydantoin that is obtained by the refining method described therein.
  • Patent Literature 1 to 4 or Non Patent Literature 1 suggests that the halohydantoin compound should be dried in a two step process to provide a halohydantoin compound in high purity and to prevent its decomposition.
  • a halohydantoin compound is so unstable at a normal temperature that the halohydantoin compound needs to be refrigerated for preservation. Further, when suspended in water, a halohydantoin compound gradually decomposes to liberate iodine. Furthermore, when heated in the state being a wet material containing a certain or lager amount of a mixed liquid component such as a mixture of water and an organic solvent, a halohydantoin compound problematically becomes more unstable.
  • the halohydantoin compound consequently decomposes to liberate a hydantoin compound and iodine. This undesirably causes a decrease in purity of the halohydantoin compound. Further, the iodine thus liberated undesirably causes coloring of the halohydantoin compound and corrosion of refining equipment.
  • the present invention has been made in view of the foregoing problems, and it is an object of the present invention to provide a method for producing a halohydantoin compound by removing a component such as an organic solvent from a composition containing the halohydantoin compound while inhibiting the halohydantoin compound from decomposing to invite coloring of the halohydantoin compound and corrosion of the equipment.
  • the inventors of the present invention made diligent studies and as a result found out that when a halohydantoin compound containing an organic solvent is dried at a high temperature, decomposition of the halohydatoin compound is accelerated. Consequently, the inventors of the present invention have attained the present invention.
  • a production method of the present invention is attained in view of the above object and the production method is a method for producing a halohydantoin compound by refining, in a dryer, a composition containing at least one of water and elemental halogen, an organic solvent, and the halohydantoin compound, the method including the steps of: (i) removing the organic solvent from the composition, at a temperature in a range of not less than 15°C and not greater than 50°C; and (ii) removing the at least one of the water and the elemental halogen from the composition refined in the step (i) at a temperature in a range of not greater than 90°C, wherein in the step (i) of removing the organic solvent from the composition, a content of the organic solvent is decreased to a range of not greater than 0.5 weight%, and wherein at least one of the temperature and the pressure in the dryer is set lower in the step (i) than in the step (ii), wherein the steps (i) and (
  • the used apparatus is an apparatus for producing a halohydantoin compound according to the method of the invention, the apparatus refining a composition containing at least one of water and elemental halogen, an organic solvent, and the halohydantoin compound, the apparatus including: a dryer for drying the composition so as to remove a component except the halohydantoin compound from the composition; pressure control means for controlling a pressure in the dryer; a collection tank for collecting the component removed from the composition, the collection tank being connected to the dryer via a duct; and heating means for heating the duct.
  • a recycling process of the present invention is attained in view of the above object and the recycling process is a process having the steps of refining a composition containing at least one of water and elemental halogen, an organic solvent, and a halohydantoin compound and recovering a component removed by refining, the recycling process including the steps of: (a) preparing the composition; (b) after the step (a), removing first the organic solvent from the composition and then at least one of the water and the elemental halogen from the composition; and (c) collecting the component removed in the step (b) and recovering the component collected, for use in the step (a) to be newly carried out, wherein step (b) includes the steps of: (i) removing the organic solvent from the composition, at a temperature in a range of not less than 15°C and not greater than 50°C; and (ii) removing at least one of the water and the elemental halogen from the composition refined in the step (i), at a temperature in a range not greater than 90°C, where
  • a halohydantoin compound obtained by the method of the present invention may be arranged so as to have a water content of not greater than 3 weight%.
  • the present invention advantageously makes it possible to produce a halohydantoin compound by removing a component such as an organic solvent from a composition containing the halohydantoin compound while inhibiting the halohydantoin compound from decomposing to invite coloring of the halohydantoin compound and corrosion of equipment.
  • Fig. 1 is a view schematically illustrating an arrangement of one embodiment of a production apparatus according to the present invention.
  • a production method of the present invention is for producing a halohydantoin compound by refining, in a dryer, a composition containing at least one of water and elemental halogen, an organic solvent, and the halohydantoin compound, and includes the first step (i) of removing the organic solvent from the composition, at a temperature in a range of not less than 15°C and not greater than 50°C and the second step (ii) of removing the at least one of the water and the elemental halogen from the composition refined in the first step at a temperature in a range of not greater than 90°C, wherein in the step (i) of removing the organic solvent from the composition, a content of the organic solvent is decreased to a range of not greater than 0.5 weight%, and wherein at least one of the temperature and the pressure in the dryer is set lower in the step (i) than in the step (ii), wherein the steps (i) and (ii) are performed under a reduced pressure, and wherein the halohy
  • the halohydantoin compound is unstable when the halohydantoin compound is in the form of a wet material containing a liquid component to a certain extent.
  • a method for drying this wet material has been provided.
  • the wet material is dried by heating under a reduced pressure so that the wet material is refined, the halohydantoin compound becomes more unstable.
  • the halohydantoin compound is decomposed. Consequently, the hydantoin compound and elemental halogen are liberated. This decreases a purity of the halohydantoin compound.
  • the halohydantoin compound is colored by thus liberated elemental halogen.
  • the inventors of the present invention have made diligent studies. As a result, the inventors of the present invention found out that when a halohydantoin compound containing an organic solvent and elemental halogen is dried at a high temperature under a reduced pressure, decomposition of the halohydantoin compound is accelerated. The inventors of the present invention have consequently attained the present invention.
  • a composition that is a subject of treatment contains (i) at least one of water and elemental halogen, (ii) an organic solvent, and (iii) a halohydantoin compound.
  • the other components except the halohydantoin compound in the composition, that is, the water, the elemental halogen, and the organic solvent each are a substance whose vapor pressure at 25°C is not less than 35 Pa.
  • a lower limit value is preferably 2 weight%, more preferably 5 weight%, or even more preferably 8 weight%, while an upper limit value is preferably 50 weight%, more preferably 45 weight%, or even more preferably 40 weight%.
  • a composition whose content of a liquid component including water and the organic solvent is not less than 2 weight% and not greater than 50 weight%.
  • a composition containing the other components in the above range it is possible to produce a halohydantoin compound by removing a component such as an organic solvent from a composition containing the halohydantoin compound, while inhibiting the halohydantoin compound from decomposing to invite coloring of the halohydantoin compound and corrosion of equipment.
  • composition in the present specification indicates a composition containing a liquid component in the above range and may also be called a "wet material”. Further, a compound containing less than 5 weight% of the liquid component as a result of treatment according to the production method of the present invention may be simply referred to as a halohydantoin compound.
  • the halohydantoin compound is represented by the following chemical formula I.
  • a combination of R 1 , R 2 , X 1 and X 2 may be any combination as long as the above range is satisfied.
  • halohydantoin compound encompass 1-bromohydantoin, 1-iodohydantoin, 3-bromohydantoin, 3-iodohydantoin, 1,3-dibromohydantoin, 1,3-diiodo hydantoin, 1-bromo-5-methylhydantoin, 1-iodo-5-methylhydantoin, 3-bromo-5-methylhydantoin, 3-iodo-5-methylhydantoin, 1,3-dibromo-5-methylhydantoin, 1,3-diiodo-5-methyl-hydantoin, 1-bromo-5,5-dimethylhydantoin, 1-iodo-5,5-dimethylhydantoin, 3-bromo-5,5-dimethylhydantoin, 3-iodo-5,5-dimethylhydantoin, 1,3-diodimethylhydan
  • halohydantoin compounds contained in the composition may be identical in composition or alternatively, the above-described plurality of types of composition of the halohydantoin compound may be mixedly present in the composition.
  • a method for obtaining the halohydantoin compound is not particularly limited, but the halohydantoin compound may be synthesized according to a conventionally known method.
  • One example of a method for synthesizing the halohydantoin compound includes the step of reacting a hydantoin compound and elemental halogen in the presence of a base in an aqueous solution. For example, by reacting a hydantoin compound and an alkali metal salt (NaOH or KOH) with each other, a hydantoin metal salt is prepared.
  • this hydantoin metal salt is reacted with iodine monochloride (ICl) or iodine monobromide (IBr).
  • ICl iodine monochloride
  • IBr iodine monobromide
  • the elemental halogen for example, at least one kind from among iodine, bromine and chlorine can be employed.
  • organic solvent for example, at least one kind of the following organic solvents can be employed: an ester solvent, an aromatic solvent, an ether solvent and a chlorine solvent each having a boiling point in a range of not less than 30°C and not greater than 200°C.
  • ester solvent encompass methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, sec-butyl acetate, tert-butyl acetate, pentyl acetate, hexyl acetate, methyl propionate, ethyl propionate, propyl propionate, butyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, and butyl butyrate.
  • aromatic solvent examples include benzene, toluene, ethyl benzene, propyl benzene, cumene, butyl benzene, isobutyl benzene, sec-butyl benzene, tert-butyl benzene, o-xylene, m-xylene, p-xylene, mesitylene, 1,2,3-trimethyl benzene, 1,2,4-trimethyl benzene, o-cymene, m-cymene, and p-cymene.
  • ether solvent encompass diethyl ether, dipropyl ether, isopropyl ether, methyl-tert-butyl ether, methyl cyclopentyl ether, dibutyl ether, anisole, ethyl phenyl ether, tetrahydrofuran, tetrahydropyran, and 1,4-dioxane.
  • chlorine solvent encompass chloropropane, chlorobutane, chloropentane, chlorohexane, chloroheptane, chlorooctane, dichloromethane, 1,2-dichloroethane, 1,2-dichloropropane, 1,3-dichloropropane, 2,2-dichloropropane, 1,2-dichlorobutane, 1,3-dichlorobutane, 1,4-dichlorobutane, chloroform, 1,1,1-trichloroethane, 1,1,2-trichloroethane, 1,1,1,2-tetrachloro ethane, 1,1,2,2-tetrachloroethane, 1,2,3-trichloropropane, and carbon tetrachloride.
  • Fig. 1 is a view schematically illustrating one embodiment of a production apparatus of the present invention.
  • the production apparatus 10 is arranged to include a dryer 1, a collection tank 2 and a pressure reducing pump (pressure control means) 3.
  • the dryer 1 is for drying a composition (hereinafter, referred to as a "wet material") containing at least one of water and elemental halogen, an organic solvent, and a halohydantoin compound.
  • a composition hereinafter, referred to as a "wet material”
  • the purity of the halohydantoin compound can be increased by first reducing the pressure in the dryer 1, and then drying the wet material by heating while rotating the dryer 1 and thereby removing a component except the halohydantoin compound.
  • the dryer 1 includes a container in which the wet material is contained, and is arranged so that the interior of the container can be heated with hot water running around the container. Further, a pressure in the dryer 1 is controlled by the pressure reducing pump 3 described below. Note that a method for controlling a temperature and the pressure in the dryer 1 is not limited to the above method.
  • a rotary container vacuum dryer (conical vacuum dryer, conical dryer), a rotary drum vacuum dryer (drum vacuum dryer), a vacuum belt dryer, a tray vacuum dryer or a tray reduced-pressure dryer, etc. are suitably used.
  • the rotary container vacuum dryer (conical vacuum dryer) or the rotary drum vacuum dryer (drum vacuum dryer) are preferable for the following reasons: (i) the rotary container vacuum dryer (conical vacuum dryer) or the rotary drum vacuum dryer (drum vacuum dryer) can stir contents of the dryer 1, so that drying efficiency can be improved and agglomeration and lack of uniformity in drying can be prevented; and (ii) the rotary container vacuum dryer (conical vacuum dryer) or the rotary drum vacuum dryer (drum vacuum dryer) is a compact device.
  • the dryer 1 is connected with the collection tank 2 via a duct 4a so that a gaseous component removed in the dryer 1 can be sent into the collection tank 2. Moreover, between the dryer 1 and an end of the duct 4a which end is connected to the dryer 1 (that is, a section connecting the dryer 1 and the duct 4a), a filter (filtering means, usually made of fluororesin) 6 is provided so that gas (vaporized component) to be sent to the collection tank 2 is filtered.
  • a filter filtering means, usually made of fluororesin
  • this filter 6 prevents (i) a solid substance scattered in the dryer 1 from causing blockage in a reduced pressure lines (ducts 4a and 4b) during drying and (ii) pollution or corrosion of the collection tank 2 or the pressure reducing pump 3, thereby consequently improving a collection rate of a target object.
  • the dryer 1 may be additionally provided with, for example, an inlet for introducing an inert gas into the dryer 1.
  • an inert gas may be any gas as long as the inert gas is inert with respect to the halohydantoin compound. Examples of the inert gas encompass the air, nitrogen, helium, argon, carbon dioxide, etc.
  • the duct 4a is housed in a tubular pipe (heating means, not shown) and heated by flow of the warm air through the pipe. This makes it possible to prevent a lump of iodine from blocking in the duct 4a.
  • means for heating the duct 4a is not limited to the above arrangement.
  • the production apparatus 10 is provided with manometers 5a and 5b for monitoring difference between the pressure in the dryer 1 and the pressure in the duct 4a, and a sight glass 7 for checking blockage in the duct 4a.
  • the collection tank 2 is a tank for collecting the component removed from the wet material.
  • the collection tank 2 is connected with the duct 4a so that gas discharged from the dryer 1 is sent into the collection tank 2.
  • One collection tank or a plurality of collection tanks may be provided as the collection tank(s) 2.
  • two collection tanks (2a and 2b) are provided in series with each other.
  • the collection tank 2a is arranged so that the interior of the collection tank 2a is empty and iodine contained in the gas sent in is collected in the collection tank 2a.
  • liquid for absorbing gas is contained in the collection tank 2b so that elemental halogen (i.e., bromine or chlorine) except iodine, water, an organic solvent, and iodine that has not been collected in the collection tank 2a are collected in the collection tank 2b.
  • elemental halogen i.e., bromine or chlorine
  • iodine i.e., bromine or chlorine
  • water, an organic solvent, and iodine that has not been collected in the collection tank 2a are collected in the collection tank 2b.
  • a reducing-agent containing aqueous solution or an organic solvent can be employed as the liquid contained in the collection tank 2b.
  • the interior of the collection tank 2a is empty and liquid is contained in the collection tank 2b in the present embodiment, liquid may be contained in the collection tank 2a.
  • the production apparatus 10 may be arranged to have only one collection tank, and elemental halogen except iodine, water, and an organic solvent are collected in the collection tank 2a.
  • the collection tank 2b may contain liquid, and the liquid may be circulated through the collection tank 2b by once taking the liquid out from the collection tank 2b and pouring the liquid like a shower back into the collection tank 2b.
  • the collection tank 2a may contain liquid, and the liquid may be circulated through the collection tank 2a by once taking the liquid out from the collection tank 2a and pouring the liquid like a shower back into the collection tank 2a.
  • both the collection tanks 2a and 2b may contain liquid, and the liquid may be circulated through the collection tanks 2a and 2b by once taking the liquid out from the collection tanks 2a and 2b and pouring the liquid like a shower back into the collection tanks 2a and 2b.
  • the pressure reducing pump 3 is a pump for controlling the pressure in the dryer 1.
  • the pressure reducing pump 3 is connected to the collection tank 2 via the duct 4b, so that the pressure reducing pump 3 reduces the pressure in the dryer 1 via the collection tank 2 and the ducts 4a and 4b. Note that the reduced pressure in the dryer 1 is returned to an ordinary pressure, for example, with nitrogen.
  • the production apparatus of the present embodiment may be arranged to include, for example, a control system.
  • various types of processing in the production apparatus can be automated by use of the control system.
  • the first step of the production method of the present invention is the step of removing the organic solvent from the wet material in the dryer 1.
  • the wet material is put in the dryer 1.
  • the pressure in the dryer 1 is reduced to a pressure lower than the atmospheric pressure by the pressure reducing pump 3.
  • the temperature in the dryer 1 is increased by heating and thereby, the organic solvent is vaporized and removed from the wet material.
  • the wet material is dried by employing a conical vacuum dryer while the conical vacuum dryer is being rotated.
  • the method for drying the wet material is not limited to this arrangement.
  • the lower limit value of the temperature in the dryer 1 in the first step is 15°C, preferably 25°C, or more preferably 35°C, while the upper limit value of the temperature in the dryer 1 in the first step is 50°C.
  • the lower limit value of the pressure in the dryer 1 in the first step is preferably 0.1 kPa, more preferably 0.3 kPa, or even more preferably 0.5 kPa, while the upper limit value of the pressure in the dryer 1 in the first step is preferably 20 kPa, more preferably 15 kPa, or even more preferably 10 kPa.
  • the organic solvent removed from the dryer 1 is sent into the collection tank 2a and 2b via the duct 4a.
  • the interior of the collection tank 2a is empty while the collection tank 2b contains liquid. Therefore, the organic solvent sent through the duct 4a is collected in the collection tank 2b.
  • the first step at least one of the temperature and the pressure is set lower than that in the second step.
  • the halohydantoin compound containing the organic solvent and elemental halogen is dried at a high temperature under a reduced pressure, decomposition of the halohydantoin compound is accelerated. This decreases the purity of the halohydantoin compound and/or causes coloring of the halohydantoin compound or corrosion of equipment due to the liberated elemental halogen (mainly, iodine).
  • the organic solvent and elemental halogen are removed at a lower temperature under a lower pressure. This makes it possible to prevent decomposition of the halohydantoin compound from accelerating.
  • a content of the organic solvent or elemental halogen contained in the wet material becomes not more than a predetermined value can be used as a criterion for determining when to end the first step.
  • a criterion can be set as appropriate according to properties and states of what to be prepared. For example, whether or not the content of the organic solvent in the composition (hereinafter, "crude dried product") refined in the first step becomes not greater than 0.5 weight%, or preferably not greater than 0.2 weight% can be used as a criterion for determining when to end the first step.
  • decomposition of the halohydantoin compound can also be prevented at the temperature set in the second step.
  • the content of elemental halogen in the crude dried product becomes preferably not greater than 0.75 weight% or more preferably, not greater than 0.5 weight% can be used as a criterion for determining when to end the first step.
  • the content of elemental halogen in the composition refined in the first step is not greater than 0.75 weight%
  • decomposition of the halohydantoin compound can also be prevented at the temperature set in the second step.
  • the reduced pressure in the dryer 1 may be returned to an ordinary pressure and then the pressure is reduced again when the step shifts to the second step.
  • the second step in the production method of the present invention is the step of removing at least one of water and elemental halogen from the crude dried product having been refined in the dryer 1.
  • the pressure in the dryer 1 containing the crude dried product is reduced by use of the pressure reducing pump 3 and the temperature in the dryer 1 is increased by heating while the dryer 1 is being rotated. At this time, at least one of the temperature and the pressure in the dryer 1 is set higher than that in the first step. This makes it possible to remove at least one of water and elemental halogen from the crude dried product.
  • the lower limit value of the temperature in the dryer 1 in the second step is preferably 60°C, more preferably 70°C, or even more preferably 75°C, while the upper limit value of the temperature in the dryer 1 in the second step is 90°C.
  • the lower limit value of the pressure in the dryer 1 in the second step is preferably 0.1 kPa, more preferably 0.3 kPa, or even more preferably 0.5 kPa, while the upper limit of the pressure in the dryer 1 in the second step is preferably 25 kPa, more preferably 20 kPa, or even more preferably 15 kPa.
  • the water and elemental halogen removed from the dryer 1 is sent into the collection tanks 2a and 2b via the duct 4a.
  • iodine among elemental halogens is collected in the empty collection tank 2a.
  • elemental halogens except iodine and water are collected in the collection tank 2b containing liquid.
  • the second step at least one of the temperature and the pressure is set higher than that in the first step. This makes it possible to remove mainly water and elemental halogen from the crude dried product. Because the crude dried product is dried by heating at a sufficiently high temperature under a sufficiently high pressure, the halohydantoin compound can be made into a more stable dried product. Further, when the second step is carried out, the organic solvent has already been removed from the crude dried product. Accordingly, even when the drying by heating is carried out at a high temperature, acceleration of decomposition of the halohydantoin compound is suppressed. This makes it possible to produce a highly-pure halohydantoin compound that is less colored.
  • elemental halogen Even in a case where the method of the present invention is employed, part of the halohydantoin compound may be decomposed during drying and consequently, elemental halogen may be produced. However, according to the present invention, thus produced elemental halogen can also be suitably removed during drying. Accordingly, even in the case of a composition containing elemental halogen initially (i.e. in the wet material), the elemental halogen can be suitably removed by the method of the present invention and a highly-pure halohydantoin compound can be obtained by refinement.
  • a content of water contained in the crude dried product becomes not more than a predetermined value can be used as a criterion for determining when to end the second step.
  • a criterion can be set as appropriate according to properties and states of what to be prepared. For example, whether or not the content of water in the dried product in the second step becomes preferably not greater than 3.0 weight%, more preferably not greater than 2.0 weight%, or most preferably 1.0 weight% can be used as a criterion for determining when to end the second step.
  • a halohydantoin compound which is suitably dried so that an organic solvent and elemental halogen are removed, and (ii) which has the water content of not greater than 3 weight%.
  • the halohydatoin compound can be stored without deterioration in purity for not less than one year by refrigeration storage at the temperature of 5°C.
  • the method of the present invention for producing a halohydantoin compound may further include an additional step following the end of the second step.
  • the additional step may be, for example, the step of further removing at least one of water and elemental halogen, or an organic solvent from the composition.
  • the present invention also provides a process for recycling the organic solvent and the elemental halogen that are removed from the composition and collected in the above-described production method.
  • a recycling process of the present invention is a process having the steps of refining a composition containing at least one of water and elemental halogen, an organic solvent, and a halohydantoin compound and recovering a component removed by refining, the recycling system including the steps of: (a) preparing the composition; (b) after the step (a), removing first the organic solvent from the composition and then at least one of the water and the elemental halogen from the composition; and (c) collecting the component removed in the step (b) and recovering the component collected, for use in the step (a) to be newly carried out, wherein step (b) includes the steps of: (i) removing the organic solvent from the composition, at a temperature in a range of not less than 15°C and not greater than 50°C; and (ii) removing at least one of the water and the elemental halogen from the composition refined in the step (i), at a temperature in a range of not greater than 90°C and wherein in the step (i) at least one of the
  • the step (a) is for preparing a composition containing at least one of water and elemental halogen, an organic solvent, and a halohydantoin compound.
  • the composition prepared here may be the wet material in the description of the production method of the present invention. As a method for preparing the composition, it is possible to employ the synthesis method described above.
  • the step (b) is for removing, after the step (a), first the organic solvent from the composition and then at least one of the water and the elemental halogen. Therefore, to this step (b), procedures for the first step and the second step in the production method of the present invention are applied.
  • step (b) includes the steps of: (i) removing the organic solvent from the composition, at a temperature in a range of not less than 15°C and not greater than 60°C; and (ii) removing at least one of the water and the elemental halogen from the composition refined in the step (i); and wherein in the step (i) at least one of the temperature and the pressure in the dryer is set lower in the step (i) than in the step (ii), and the content of the organic solvent is decreased to a range of not greater than 0.5 weight%.
  • the step (c) is for collecting the component removed in the step (b) and recovering the component collected, for use in the step (a) to be newly carried out.
  • the method for collecting the component removed it is possible to employ the method discussed in the production method of the present invention. Further, how the component is recovered is not particularly limited. For example, it is possible to provide in advance ducts respectively for taking out the organic solvent and the elemental halogen so that the ducts are connected to the collection tanks 2a and 2b of the production apparatus 10 as illustrated in Fig. 1 , and take out the organic solvent and the elemental halogen through the ducts. This makes it possible to recycle thus recovered component in the step of preparing a composition to be newly carried out.
  • the step (a) of preparing a composition to be newly carried out here indicates the step (a) of newly preparing a composition after the step (c) of recovering the component, that is, the step of synthesizing a wet material containing a halohydantoin compound.
  • the composition can be synthesized by use of the component recovered in the step (c) of recovering the component.
  • the content of the organic solvent is decreased to a range of not greater than 0.5 weight%.
  • the elemental halogen is removed so that a content of the elemental halogen is decreased to a range of not greater than 0.75 weight%.
  • At least one of the temperature and the pressure in the dryer is set lower in the first step (i) than in the second step (ii).
  • the temperature in the first step (i) is in a range of not less than 15°C and not greater than 50°C, and, preferably, the temperature in the second step (ii) is in a range of not less than 60°C and not greater than 90°C.
  • the pressure in the first step (i), is in a range of not less than 0.1 kPa and not greater than 20 kPa; and in the second step (ii), the pressure is in a range of not less than 0.1 kPa and not greater than 25 kPa.
  • the organic solvent can suitably be at least one selected from among an ester solvent, an aromatic solvent, an ether solvent, and a chlorine solvent each having a boiling point in a range of not less than 30°C and not greater than 200°C under an atmospheric pressure.
  • the elemental halogen can suitably be at least one selected from among iodine, bromine and chlorine.
  • the halohydantoin compound is a compound represented by the chemical formula I above.
  • the production apparatus to be used for producing a halohydantoin compound according to the method of the present invention further includes filtering means for filtering the component vaporized, the filtering means being connected to a connecting section between the dryer and the duct.
  • the collection tank contains liquid for absorbing the component vaporized.
  • the liquid is either a reducing-agent containing aqueous solution or an organic solvent.
  • Quantitative determination of 1,3-diiodo-5,5-dimethylhydantoin was performed by a titration method with a 0.1 N aqueous solution of silver nitrate, and quantitative determination of butyl acetate was performed by an internal reference method of gas chromatography.
  • Quantitative determination of elemental iodine extracted from a sample with use of chloroform was performed by a silver nitrate titration method.
  • the water content was a value obtained by subtracting the content of elemental iodine from the content of a volatile substance.
  • This content of the volatile substance was obtained by measuring a decrease in mass of a sample in a case where the sample was subjected to 2-hour drying at 105°C under the atmospheric pressure according to " First Method: Method for Drying by Heating under Atmospheric Pressure" in JIS-K0067-1992 4.1.4(1) .
  • composition containing 1,3-diiodo-5,5-dimethylhydantoin (halohydantoin compound) was produced by the following procedures.
  • the wet material (composition) thus obtained containing 1,3-diiodo-5,5-dimethylhydantoin had a weight of 83.3 kg.
  • Thus obtained wet material contained 73.3 kg (88.0% by weight) of 1,3-diiodo-5,5-dimethylhydantoin, 1.3 kg (1.6% by weight) of elemental iodine, 7.3 kg (8.8% by weight) of water, and 0.8 kg (1.0% by weight) of butyl acetate.
  • Example 1 a halohydatoin compound was produced by drying, according to the following method, a halohydantoin-compound-containing composition obtained by the method of Production Example 1.
  • a wet material of 1,3-diiodo-5,5-dimethylhydantoin obtained by the method of Production Example 1 was put in a conical vacuum dryer having an internal capacity of 1000 L and the first step was carried out.
  • the wet material contained 1,3-diiodo-5,5-dimethylhydantoin whose weight was 73.3 kg (88.0 weight%), elemental iodine whose weight was 1.3 kg (1.6 weight%), water whose weight was 7.3 kg (8.8 weight%) and butyl acetate whose weight was 0.8 kg (1.0 weight%).
  • the criterion based on the organic solvent for determining the end of the first step was satisfied because the first refined product contained 91.0 weight% of 1,3-diiodo-5,5-dimethylhydantoin, 0.38 weight% of elemental iodine, and 0.1 weight% of butyl acetate.
  • the second step was carried out. More specifically, reduction of the pressure was started and after the degree of reduced pressure reaches a given level, a conical vacuum dryer was rotated. At the same time, a heat medium was provided through the jacket of the conical vacuum dryer. Then, drying was restarted. One hour after this restart of drying, the temperature in the dryer reached 59.6°C. Thereafter, drying was further carried out for three hours. During this 3-hour drying, the temperature in the dryer was in a range of 59.6°C to 66.8°C and the pressure in the dryer was in a range of 4.9 kPa to 6.0 kPa.
  • Examples 2 through 4 by use of a wet material obtained in the same manner as in Production Example 1, refinement was carried out in the same manner as in Example 1. Note that Examples 2 through 4 are different from Example 1 in temperature, pressure, and drying time set for each of the first step and the second step. Table 1 shows respectively set values and respective purities of refined products obtained as a result of thus set values.
  • Example 5 a halohydantoin compound was produced by drying a halohydantoin-compound-containing composition synthesized in the above-described Production Example 1. The drying in Example 5 was carried out by the following method.
  • the first refined product contained 1,3-diiodo-5,5-dimethylhydantoin whose weight was 236.5 kg (90.9 weight%), water whose weight was 21.0 kg (8.1 weight%), and butyl acetate whose weight was 0.2 kg (0.1 weight%).
  • a first collection tank 0.1 kg of elemental iodine was collected, while in a second collection tank, 6.9 kg of water and 3.7 kg of butyl acetate were collected.
  • the conical vacuum dryer was first rotated and reduction of pressure was started. At the same time, a heat medium was provided through the jacket of the conical vacuum dryer. Then, drying was carried out for 6.5 hours. During the drying, the pressure in the dryer was in a range of 2.1 kPa to 10.5 kPa. After cooling water was provided through the jacket of the conical vacuum dryer and the temperature in the dryer was cooled down to 30°C, the reduced pressure was returned to an ordinary pressure with nitrogen and a second refined product (dried product) was taken out from the conical vacuum dryer. The weight of thus obtained second refined product was 239.2 kg.
  • the second refined product contained 1,3-diiodo-5,5-dimethylhydantoin whose weight was 230.5 kg (96.4 weight%) and water whose weight was 2.0 kg (0.8 weight%).
  • the color of this second refined product was pale yellow.
  • 2.0 kg of elemental iodine was collected, while in the second collection tank, 19 kg of water was collected.
  • the elemental iodine collected in the first collection tank was treated with alkaline sulfite aqueous solution and recovered as iodine salts and further recovered as elemental iodine by chlorine oxidation of the iodine salts.
  • Example 6 a halohydantoin compound was obtained by drying a halohydantoin-compound-containing composition obtained in the same manner as in the Production Example 1. This drying in Example 6 was carried out by the following method.
  • the conical vacuum dryer was first rotated, and reduction of pressure was started. At the same time, a heat medium was provided through a jacket of the conical vacuum dryer. Then, drying was carried out for 6 hours. During the drying, the pressure in the dryer was in a range of 3.8 kPa to 7.1 kPa. Subsequently, the reduced pressure was returned to an ordinary pressure with nitrogen and part of a first refined product (crude dried product) was taken out from the conical vacuum dryer and analyzed. As a result, it was found that the first refined product contained 90.9 weight% of 1,3-diiodo-5,5-dimethylhydantoin, 8.1 weight% of water, and 0.1 weight% of butyl acetate. In a first collection tank, 0.1 kg of elemental iodine was collected, while in a second collection tank, 6.9 kg of water and 3.7 kg of butyl acetate were collected.
  • the conical vacuum dryer was first rotated and reduction of pressure was started. At the same time, a heat medium was provided through the jacket of the conical vacuum dryer. Then, drying was carried out for 6 hours. During the drying, the pressure in the dryer was in a range of 3.7 kPa to 9.4 kPa. After cooling water was provided through the jacket of the conical vacuum dryer and the temperature in the dryer was cooled down to 30°C, the reduced pressure was returned to an ordinary pressure with nitrogen and a second refined product (dried product) was taken out from the conical vacuum dryer. The weight of thus obtained second refined product was 239.2 kg.
  • the second refined product contained 1,3-diiodo-5,5-dimethylhydantoin whose weight was 230.5 kg (96.1 weight%) and water whose weight was 2.0 kg (0.8 weight%).
  • the color of this second refined product was pale yellow.
  • a first collection tank 2.0 kg of elemental iodine was collected, while in a second collection tank, 19 kg of water was collected.
  • the elemental iodine collected in the first collection tank was treated with alkaline sulfite aqueous solution and recovered as iodine salts and further recovered as elemental iodine by chlorine oxidation of the iodine salts.
  • Example 7 a second refined product was obtained by refining, in the same manner as in Example 1, a halohydantoin-compound-containing composition obtained in the same manner as in Production Example 1.
  • second refined product contained 1,3-diiodo-5,5-dimethylhydantoin whose purity was 96.9 weight%, and 0.4 weight% of water. Further, this second refined product was analyzed by NMR.
  • the second refined product contained 1,3-diiodo-5,5-dimethylhydantoin, 1-iodo-5,5-dimethylhydantoin, 3-iodo-5,5-dimethylhydantoin and 5,5-dimethylhydantoin, and a weight ratio of 1,3-diiodo-5,5-dimethylhydantoin : 1-iodo-5,5-dimethylhydantoin : 3-iodo-5,5-dimethylhydantoin : 5,5-dimethylhydantoin was 96.9:1.1:2.0:0.0.
  • Comparative Example 1 In Comparative Example 1, first, 17.6 kg of 1,3-diiodo-5,5-dimethylhydantoin obtained in the same manner as in Production Example 1 was fed into a conical vacuum dryer having an internal capacity of 200 L. This 1,3-diiodo-5,5-dimethylhydantoin had a purity of 88.7% . Then, the conical vacuum dryer was rotated and reduction of pressure was started. At the same time, heated water whose temperature was controlled in a range of 72°C to 74°C was provided through a jacket of the conical dryer. Then, drying was carried out for 9 hours. During the drying, the pressure in the dryer was in a range of 7.2 kPa to 8.2 kPa.
  • the content of 3-diiodo-5,5-dimethylhydantoin was found to be 91.1 weight%.
  • the dried product of 1,3-diiodo-5,5-dimethylhydantoin was measured by dry sieving. As a result, it was found that 80% of the dried product had a particle size of less than 8 mm, 9% of the dried product had a particle size in a range of 8 mm to 15 mm, and 11% of the dried product had a particle size of more than 15 mm.
  • Comparative Example 2 a halohydantoin-compound-containing composition obtained in the same manner as in Production Example 1 was refined in the same manner as in Comparative Example 1 and thereby, a dried product was obtained.
  • dried product ununiformly contained a solid colored to dark brown and black elemental iodine as in Comparative Example 1.
  • a purity of 1,3-diiodo-5,5-dimethylhydantoin was 91.0 weight%. Further, this dried product was analyzed by NMR.
  • the dried product contained 1,3-diiodo-5,5-dimethylhydantoin, 1-iodo-5,5-dimethylhydantoin, 3-iodo-5,5-dimethylhydantoin, and 5,5-dimethylhydantoin, and a weight ratio of 1,3-diiodo-5,5-dimethylhydantoin : 1-iodo-5,5-dimethylhydantoin : 3-iodo-5,5-dimethylhydantoin : 5,5-dimethylhydantoin was 82.3:4.5:12.4:0.8.
  • the present invention can be suitably applied to a method for producing a halohydantoin compound to be used as a sensitizer for a photograph or the like, or a halohydantoin compound used as a halogenating agent or an oxidizing agent for use in a production process of medical products, agricultural chemicals, chemical products, etc.

Claims (14)

  1. Procédé de production d'un composé d'halo-hydantoïne par raffinage, dans un séchoir, d'une composition contenant au moins l'un de l'eau et d'un halogène élémentaire, un solvant organique et le composé d'halo-hydantoïne, le procédé comprenant les étapes suivantes :
    (i) l'élimination du solvant organique présent dans la composition, à une température située dans une plage allant de 15 °C minimum à 50 °C maximum ; et
    (ii) l'élimination de l'au moins l'un de l'eau et de l'halogène élémentaire présents dans la composition raffinée à l'étape (i), à une température située dans une plage n'excédant pas 90 °C,
    à l'étape (i) d'élimination du solvant organique présent dans la composition, la teneur en solvant organique étant abaissée jusqu'à une plage n'excédant pas 0,5 % en poids, et au moins l'une de la température et de la pression dans le séchoir étant ajustée à une valeur plus faible à l'étape (i) qu'à l'étape (ii)
    les étapes (i) et (ii) étant réalisées à une pression réduite, et
    le composé d'halo-hydantoïne étant un composé représenté par la formule chimique I :
    Figure imgb0006
     où :
    R1 et R2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène, un groupe hydrocarboné aliphatique en C1 à C10 substitué ou non substitué, un groupe hydrocarboné alicyclique en C3 à C10 substitué ou non substitué, ou un groupe aryle ou un groupe aralkyle en C6 à C10 substitué ou non substitué, et
    X1 et X2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène ou un atome d'halogène,
    à l'exclusion d'un composé d'halo-hydantoïne dans lequel X1 et X2 représentent tous deux l'hydrogène.
  2. Procédé selon la revendication 1, dans lequel, à l'étape (i) d'élimination du solvant organique présent dans la composition, l'halogène élémentaire est éliminé de manière à abaisser la teneur en halogène élémentaire jusqu'à une plage n'excédant pas 0,75 % en poids.
  3. Procédé selon la revendication 1 ou 2, dans lequel la température à l'étape (ii) se situe dans une plage allant de 60 °C minimum à 90 °C maximum.
  4. Procédé selon l'une quelconque des revendications 1 à 3, dans lequel :
    à l'étape (i), la pression se situe dans une plage allant de 0,1 kPa minimum à 20 kPa maximum ; et
    à l'étape (ii), la pression se situe dans une plage allant de 0,1 kPa minimum à 25 kPa maximum.
  5. Procédé selon l'une quelconque des revendications 1 à 4, dans lequel :
    le solvant organique est au moins un solvant choisi parmi un solvant ester, un solvant aromatique, un solvant éther et un solvant chloré, ayant chacun un point d'ébullition situé dans une plage allant de 30 °C minimum à 200 °C maximum à la pression atmosphérique.
  6. Procédé selon l'une quelconque des revendications 1 à 5, dans lequel l'halogène élémentaire est au moins un halogène choisi parmi l'iode, le brome et le chlore.
  7. Procédé selon la revendication 1, dans lequel, dans la formule chimique I,
    R1 et R2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène ou un groupe hydrocarboné aliphatique en C1 à C8,
    X1 et X2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène, le brome ou l'iode, à l'exclusion d'un composé d'halo-hydantoïne dans lequel X1 et X2 représentent tous deux l'hydrogène.
  8. Procédé selon la revendication 1, dans lequel, dans la formule chimique I,
    R1 et R2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène ou un groupe méthyle,
    X1 et X2 sont soit identiques, soit différents l'un de l'autre, et représentent chacun indépendamment l'hydrogène ou l'iode, à l'exclusion d'un composé d'halo-hydantoïne dans lequel X1 et X2 représentent tous deux l'hydrogène.
  9. Procédé selon la revendication 1, dans lequel, dans la formule chimique I,
    R1 et R2 sont tous deux des groupes méthyle ; et
    X1 et X2 sont tous deux l'iode.
  10. Utilisation d'un appareil pour produire un composé d'halo-hydantoïne par le procédé selon l'une quelconque des revendications 1 à 9, l'appareil raffinant une composition contenant au moins l'un de l'eau et d'un halogène élémentaire, un solvant organique et le composé d'halo-hydantoïne, l'appareil comprenant :
    un séchoir pour sécher la composition de manière à éliminer de la composition un constituant autre que le composé d'halo-hydantoïne ;
    un moyen de régulation de la pression pour réguler la pression dans le séchoir ;
    un réservoir collecteur pour collecter le constituant éliminé de la composition, le réservoir collecteur étant raccordé au séchoir par l'intermédiaire d'une conduite ; et
    un moyen de chauffage pour chauffer la conduite.
  11. Utilisation de l'appareil selon la revendication 10, comprenant en outre un moyen de filtration pour filtrer le composant évaporé, le moyen de filtration étant raccordé à une section de raccordement entre le séchoir et la conduite.
  12. Utilisation de l'appareil de production selon la revendication 10 ou 11, dans laquelle le réservoir collecteur contient un liquide pour absorber le constituant évaporé.
  13. Utilisation de l'appareil de production selon la revendication 12, dans laquelle le liquide est soit une solution aqueuse contenant un réducteur, soit un solvant organique.
  14. Processus de recyclage comprenant les étapes de raffinage d'une composition contenant au moins l'un de l'eau et d'un halogène élémentaire, un solvant organique, et un composé d'halo-hydantoïne, et de récupération d'un constituant éliminé par raffinage, le processus de recyclage comprenant les étapes suivantes :
    (a) la formulation de la composition ;
    (b) après l'étape (a), l'élimination du solvant organique présent dans la composition, puis d'au moins l'un de l'eau et de l'halogène élémentaire présents de la composition ; et
    (c) la collecte du constituant éliminé à l'étape (b) et la récupération du constituant collecté, en vue de son utilisation à l'étape (a), à effectuer de nouveau,
    l'étape (b) comprenant le procédé selon l'une quelconque des revendications 1 à 9.
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CN104854095A (zh) 2015-08-19
US20170056786A1 (en) 2017-03-02
EP2937338A4 (fr) 2016-05-04
JP6377531B2 (ja) 2018-08-22
EP2937338A1 (fr) 2015-10-28
US20170057927A1 (en) 2017-03-02
CN104854095B (zh) 2018-01-30
WO2014097788A1 (fr) 2014-06-26
US20150299137A1 (en) 2015-10-22

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